EP2451427B1 - Uv filter combinations comprising benzylidene malonates - Google Patents

Uv filter combinations comprising benzylidene malonates Download PDF

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Publication number
EP2451427B1
EP2451427B1 EP10730140.0A EP10730140A EP2451427B1 EP 2451427 B1 EP2451427 B1 EP 2451427B1 EP 10730140 A EP10730140 A EP 10730140A EP 2451427 B1 EP2451427 B1 EP 2451427B1
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EP
European Patent Office
Prior art keywords
mbm
bis
methyl
diethylamino
filter
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EP10730140.0A
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German (de)
English (en)
French (fr)
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EP2451427A2 (en
Inventor
Julie Grumelard
Thomas Ehlis
Markus Hansch
Myriam Sohn
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BASF SE
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BASF SE
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair

Definitions

  • the present invention relates to the use of specific UV filter combinations comprising benzylidene malonates for cosmetic preparations.
  • UV radiation is harmful to human skin.
  • UV-B radiation (about 290 to about 320 nm) is responsible for sunburn and can cause skin cancer.
  • UV-A radiation (about 320 to about 400 nm) while producing tanning of the skin, contributes also to sunburn and the induction of skin cancers.
  • UV-A radiation may be aggravated by UV-A radiation.
  • an effective sunscreen formulation preferably comprises both at least one UV-A and UV-B filter and a broad band UV filter covering the full range from about 290nm to about 40 nm to prevent the human skin from the damage of sunlight.
  • UV filters Besides their screening power on solar radiation UV filters must also have good resistance to water and perspiration and also satisfactory photostability.
  • UV filters like Butyl Methoxydibenzoylmethane (sold under the tradename "Parsol 1789” by DSM) which have the particularity and also the disadvantage of being solid at ambient temperature.
  • their use in sunscreen cosmetic compositions implies certain constraints in terms of their formulation and their use, in particular the selection of specific suitable cosmetic solvents that afford a proper solubility of these UV filters.
  • a UV filter should show high solubility in common cosmetic oils or should be a good solvent for other UV filters that show poor oil solubility.
  • UV absorber should be included in cosmetic sun care products without any impact on the sensorial characteristic of the emulsion. For that reason the optimal distribution of the UV absorber within the hydro-lipid film left on the skin after spreading should be guaranteed.
  • US 5,670,140 discloses dialkylbenzalmalonates (benzylidene malonates) used as stabilisers for dibenzoylmethane derivatives.
  • EP 0 848 947 A1 discloses a cosmetic composition comprising a combination of i) a dibenzoylmethane derivative, ii) a triazine derivative and iii) a dialkyl benzalmalonate.
  • EP 0 848 947 A1 shows a composition comprising diisoamyl methoxybenzalmalonate together with Uvinul T150 and Parsol 1789.
  • US 4,457,911 discloses dialkyl malonates in compositions with further UV filters to provide surprising protection.
  • the dialkyl malonates include diethyl 4'-methoxybenzalmalonate.
  • FR 2 908 988 A1 discloses the photostabilisation of a dibenzoylmethane derivative with a bis-resorcinyltriazine and a silylated triazine.
  • EP 1 927 343 A1 discloses a photoprotective composition comprising a 1,3,5-triazine, a dibenzoylmethane and a silylated triazine. It is therefore an object of the present invention to find UV absorber formulations which have improved properties regarding the UV absorber. Surprisingly it has been found that specific monomeric benzylidene malonates have very good properties as cosmetic UV-B absorbers.
  • the present invention relates to a composition for use in the protection of human and animal hair and skin against UV radiation comprising a UV filter combination, comprising
  • R 1 is ethyl; propyl; or n-butyl; and R is isopropyl.
  • UV filter combination comprising:
  • Table 1 Examples of compounds of formula (1) are listed in the Table 1 below: Table 1: Examples of monomeric benzylidene malonates according to the present invention R 1 R MBM-01 methyl MBM-02 methyl MBM-03 methyl MBM-04 methyl MBM-05 methyl MBM-06 methyl MBM-07 methyl MBM-08 methyl MBM-09 methyl MBM-10 ethyl MBM-11 propyl MBM-12 n-butyl MBM-13 methyl
  • the UV filter combinations comprises
  • UV filter combinations comprising
  • UV filter combinations comprising
  • UV filter combinations comprising
  • UV filter combinations comprising
  • UV filter combinations according to the present invention UV filter Component (a) UV filter Component (b 1 ) - (b 15 ) 1 2 3 4 ⁇ 5 Combination of 3 UV filters 2 MBM BEMT DHHB Combination of 4 UV filters 6 MBM BEMT DHHB EHT BBDAPT Combination of ⁇ 5 UV filters 8 MBM BEMT DHHB EHT EHS TBT OCR DBT PBSA TiO 2 HMS DHHM BBDAPT 10 MBM MBBT DHHB BBDAPT BEMT* MBM MONOMERIC Benzylidene Malonate BEMT Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine BMBM Butyl Methoxydibenzoylmethane DBT Diethylhexyl Butamido Triazone EHT Ethylhexyl Triazone BBDAPT Bis(butylbenzoate) diaminotria
  • the benzylidene malonates are prepared in a manner known per se according to the following reaction scheme:
  • Knoevenagel condensation under conditions (a) is carried out under azeotropic removal of water in the presence of a catalyst (literature: Jones, Gurnos. Knoevenagel condensation. Organic Reactions (New York) 15, 204-599 (1967 ).
  • Solvents used in this step are for example benzene, toluene, o-xylene, m-xylene, p-xylene, chloroform, dichloromethane, ethanol, methanol, tetrahydrofurane, acetonitrile, ethyl acetate, CCl 4 , cyclohexane, n-hexane, n-pentane, or ionic liquids as for example 1-methyl-3-butyl imidazolium bromide. Mixtures of solvents can also be used.
  • the reaction temperature is preferably between 0°C and the reflux temperature of the solvent mixture, preferably between 0°C and 180°C, and more preferably between 20° and 150°C.
  • the reaction time is preferably from 5min to 72h, and more preferably from 1 to 10h.
  • the catalysts used in this reaction step are preferably primary, secondary or tertiary amines like piperidine, n-hexylamine, pyridine or triethylamine.
  • the basic amines can be used as such or in combination with an acidic compound like acetic acid, benzoic acid or HCl.
  • Suitable catalysts are any catalysts which are normally used in Knoevenagel reactions.
  • catalysts such as a salt of an organic base with an organic acid, such as piperidinium acetate.
  • the Knoevenagel condensation under conditions (b) is carried out in the presence of a tetraalkyl orthotitanate Ti(OR') (0.5 req. to 5 eq. with respect to the aldehyde) as decribed for example in K. Yamashita et al., Tetrahedron 2005, 61, 7981-7985 .
  • Solvents used in this step are alcohols R'OH, for example ethanol, methanol, isopropanol, n-propanol, n-butanol, 2-methyl-1-butanol, isobutanol, 2-butanol, 2-pentanol.
  • solvents are benzene, toluene, o-xylene, m-xylene, p-xylene, chloroform, dichloromethane, tetrahydrofurane, acetonitrile, ethyl acetate, CCl 4 , cyclohexane, n-hexane, n-pentane, or ionic liquids as for example 1-methyl-3-butyl imidazolium bromide. Mixtures of solvents can also be used.
  • the reaction temperature is preferably between -10°C and the reflux temperature of the solvent mixture, preferably between 0°C and 180°C, and more preferably between 20° and 150°C.
  • Knoevenagel condensation under conditions (c) is carried out in the presence of a titanium tetrachloride TiCl 4 (0.5 req. to 5 eq. with respect to the aldehyde) as decribed for example in W. Lehnert, Tetrahedron Letters 1970, 54, 4723-4724 or in H. Chen et al., Eur. J. Org. Chem. 2006, 2329-2335 .
  • Solvents used in this step are ethers like tetrahydrofurane, dioxane, tert-butyl-methylether, diethyl ether, or alcohols R'OH, for example ethanol, methanol, isopropanol, n-propanol, n-butanol, 2-methyl-1-butanol, isobutanol, 2-butanol, 2-pentanol.
  • solvents are benzene, toluene, o-xylene, m-xylene, p-xylene, chloroform, dichloromethane, tetrahydrofurane, acetonitrile, ethyl acetate, CCl 4 , cyclohexane, n-hexane, n-pentane, or ionic liquids as for example 1-methyl-3-butyl imidazolium bromide. Mixtures of solvents can also be used.
  • the reaction temperature is preferably between -10°C and the reflux temperature of the solvent mixture, preferably between 0°C and 180°C, and more preferably between 20° and 150°C.
  • the UV filter combination to be used according to the present invention is especially useful for the protection of organic materials that are sensitive to ultraviolet light, especially human and animal skin and hair, against the action of UV radiation.
  • Such UV filter combinations are accordingly suitable as light-protective agents in cosmetic, pharmaceutical and veterinary medicine preparations.
  • Such compounds are preferably used in the dissolved state.
  • a cosmetic preparation comprising the UV filter combination and cosmetically tolerable carriers or adjuvants are disclosed.
  • the cosmetic preparation may also comprise, in addition to the UV absorber combination, one or more further UV protective agents of the following substance classes:
  • UV absorbers described in " Sunscreens”, Eds. N.J. Lowe, N.A.Shaath, Marcel Dekker, Inc. , New York and Basle or in Cosmetics & Toiletries (107), 50ff (1992 ) also can be used as additional UV protective substances.
  • Table 3 Suitable UV filter substances and adjuvants which can be additionally used with the UV absorbers of formula MBM-01 - MBM-12 according to the present invention No. Chemical Name CAS No.
  • Helioguard 365 from Milbelle AG, isolated mycosporine like amino acids from the red alga porphyra umbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated into liposomes) 37 alpha-lipoic-acid as described in DE 10229995 38 synthetic organic polymers as described in EP 1 371 358 , [0033]-[0041] 39 phyllosilicates as described in EP 1371357 [0034]-[0037] 40 silica compounds as described in EP1371356 , [0033]-[0041] 41 inorganic particles as described in DE10138496 [0043]-[0055] 42 latex particles as described in DE10138496 [0027]-[0040] 43 1H-Benzimidazole-4,6-disulfonic acid, 2,2'-(1,4-phenylene)bis-, disodium salt ; Bisimidazylate (Neo Heliopan APC) 180898-37
  • BEMT Tinosorb S, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine encapsulated in a polymer matrix, for example in PMMA, as described in IP.com Journal (2009), 9(1B), 17 , can also be used as additional UV protective substance.
  • Merocyanine derivatives as described in WO 2004/006878 (A) and (B) can be either in E- or Z-configuration.
  • each of the above-mentioned light-protective agents can be used in admixture with the UV absorber combination to be used according to the invention. It will be understood in that connection that, in addition to the UV absorber combination to be used according to the invention, it is also possible for more than one of the additional light-protective agents to be used, for example, two, three, four, five or six further light-protective agents. Preference is given to the use of mixing ratios of UV absorbers according to the invention/further light-protective agents of from 1:99 to 99:1, especially from 1:95 to 95:1 and preferably from 10:90 to 90:10, based on weight. Of special interest are mixing ratios of from 20:80 to 80:20, especially from 40:60 to 60:40 and preferably of approximately 50:50. Such mixtures can be used, inter alia, to improve solubility or to increase UV absorption.
  • the cosmetic compositions contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of the UV absorber composition to be used according to the present invention and at least one cosmetically tolerable adjuvant.
  • the cosmetic compositions can be prepared by physically mixing the UV absorbers with the adjuvant using customary methods, for example by simply stirring together the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, for example OMC, salicylic acid isooctyl ester, inter alia.
  • the UV absorber can be used, for example, without further treatment.
  • the cosmetic compositions may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments.
  • compositions for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, super-fatting agents, pearlescent waxes, consistency regulators, thickeners, polymers, silicone compounds, fats, waxes, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like.
  • mild surfactants super-fatting agents
  • pearlescent waxes consistency regulators, thickeners, polymers, silicone compounds, fats, waxes, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film formers, swelling agents
  • Cosmetic formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations: skin-care preparations, bath preparations, skin-care preparations, cosmetic personal care preparations, foot-care preparations, light-protective preparations, skin-tanning preparations, depigmenting preparations, insect-repellents, deodorants, antiperspirants, preparations for cleansing and caring for blemished skin, hair-removal preparations in chemical form (depilation), shaving preparations, fragrance preparations, cosmetic hair-treatment preparations.
  • cosmetic compositions for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams.
  • light-protective preparations such as sun milks, lotions, creams, oils, sunblocks or tropicals
  • pretanning preparations or after-sun preparations also skin-tanning preparations, for example self-tanning creams.
  • sun protection creams, sun protection lotions, sun protection oils, sun protection milk and sun protection preparations in the form of a spray are particularly useful for sun protection cream.
  • hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays.
  • hair-washing preparations in the form of shampoos.
  • the cosmetic preparation contains from 0.1 to 15 % by weight, preferably from 0.5 to 10 % by weight, based on the total weight of the composition, of a UV absorber of formula (1) or of a mixture of UV absorbers and a cosmetically tolerable adjuvant.
  • the cosmetic preparation can be prepared by physically mixing the UV absorber or UV absorbers with the adjuvant using conventional methods, for example by simply stirring the individual components together.
  • the cosmetic preparation can be formulated as a water-in-oil or oil-in-water emulsion, as an oil-in-alcohol lotion, as a vesicular dispersion of an ionic or nonionic amphiphilic lipid, as a gel, solid stick or as an aerosol formulation.
  • the cosmetically tolerable adjuvant preferably contains from 5 to 50 % of an oil phase, from 5 to 20 % of an emulsifier and from 30 to 90 % water.
  • the oil phase can comprise any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol.
  • Preferred mono- or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
  • any conventionally usable emulsifier for example one or more ethoxylated esters of natural derivatives, for example polyethoxylated esters of hydrogenated castor oil, or a silicone oil emulsifier, for example silicone polyol; an unethoxylated or ethoxylated fatty acid soap; an ethoxylated fatty alcohol; an unethoxylated or ethoxylated sorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride.
  • the cosmetic preparation is distinguished by excellent protection of human skin against the damaging effect of sunlight.
  • UVA protection factor (UVA PF)

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  • Life Sciences & Earth Sciences (AREA)
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EP10730140.0A 2009-07-07 2010-06-29 Uv filter combinations comprising benzylidene malonates Active EP2451427B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10730140.0A EP2451427B1 (en) 2009-07-07 2010-06-29 Uv filter combinations comprising benzylidene malonates

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09164739 2009-07-07
PCT/EP2010/059181 WO2011003774A2 (en) 2009-07-07 2010-06-29 Uv filter combinations comprising benzylidene malonates
EP10730140.0A EP2451427B1 (en) 2009-07-07 2010-06-29 Uv filter combinations comprising benzylidene malonates

Publications (2)

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EP2451427A2 EP2451427A2 (en) 2012-05-16
EP2451427B1 true EP2451427B1 (en) 2018-04-25

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US (1) US9764169B2 (ja)
EP (1) EP2451427B1 (ja)
JP (2) JP5722319B2 (ja)
KR (1) KR101390075B1 (ja)
CN (1) CN102470081B (ja)
BR (1) BRPI1011916B1 (ja)
ES (1) ES2681207T3 (ja)
WO (1) WO2011003774A2 (ja)

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US20120128611A1 (en) 2012-05-24
JP2015110579A (ja) 2015-06-18
JP2012532837A (ja) 2012-12-20
EP2451427A2 (en) 2012-05-16
KR101390075B1 (ko) 2014-04-29
JP5722319B2 (ja) 2015-05-20
WO2011003774A2 (en) 2011-01-13
CN102470081B (zh) 2017-03-29
ES2681207T3 (es) 2018-09-12
BRPI1011916B1 (pt) 2017-08-01
BRPI1011916A2 (pt) 2016-04-19
US9764169B2 (en) 2017-09-19
KR20120049871A (ko) 2012-05-17
CN102470081A (zh) 2012-05-23
WO2011003774A3 (en) 2011-04-21

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